利用第一性原理模拟研究Li和LiO2的溶剂化结构和动力学及其在非水有机电解质溶剂中的转化

doi:10.1016/S1872-2067(22)64098-1

摘要/Abstract

摘要：

利用密度泛函理论计算和从头算分子动力学(AIMD)模拟研究了三种有机电解质中Li⁺和LiO₂在O₂还原时的溶剂化、扩散和转化. 这些过程对锂空气电池的性能至关重要. 除详细研究溶剂化壳层结构外, 还利用AIMD模拟推导了扩散率, 并与Blue-Moon系综方法一起探索Li⁺和O^2‒形成LiO₂以及2LiO₂歧化为Li₂O₂+O₂. 通过对比模拟结果和气相计算结果, 研究电解质对这些反应的影响, 结果表明, 对于参与这些反应的离子物种, 电解质的影响更为显著.

关键词: Li-空气电池, 氧化锂, 氧还原, 密度泛函理论, 从头算分子动力学, 溶剂化, 扩散, 歧化

Abstract:

Density functional theory calculations together with ab initio molecular dynamics (AIMD) simulations have been used to study the solvation, diffusion and transformation of Li⁺ and LiO₂ upon O₂reduction in three organic electrolytes. These processes are critical for the performance of Li-air batteries. Apart from studying the structure of the solvation shells in detail, AIMD simulations have been used to derive the diffusivity and together with the Blue Moon ensemble approach to explore LiO₂ formation from Li⁺ and O₂^- and the subsequent disproportionation of 2LiO₂ into Li₂O₂ + O₂. By comparing the results of the simulations to gas phase calculations, the impact of electrolytes on these reactions is assessed which turns out to be more pronounced for the ionic species involved in these reactions.

Key words: Li-air batteries, Li oxide, Oxygen reduction, Density functional theory, Ab initio molecular dynamics, Solvation, Diffusivity, Disproportionation

Behnaz Rahmani Didar, Axel Groß. 利用第一性原理模拟研究Li和LiO₂的溶剂化结构和动力学及其在非水有机电解质溶剂中的转化[J]. 催化学报, 2022, 43(11): 2850-2857.

Behnaz Rahmani Didar, Axel Groß. Solvation structure and dynamics of Li and LiO₂and their transformation in non-aqueous organic electrolyte solvents from first-principles simulations[J]. Chinese Journal of Catalysis, 2022, 43(11): 2850-2857.

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https://www.cjcatal.com/CN/Y2022/V43/I11/2850

图/表 7

Table 1 Interaction energies (in eV) of Li and LiO2 with electrolyte molecules obtained from DFT calculations using Eq. (1).

Electrolyte	PBE	PBE-D3	RPBE	RPBE-D3
Li
ACN (Li-N)	‒0.50	‒0.52	‒0.47	‒0.49
DMSO (Li-O)	‒0.76	‒0.79	‒0.67	‒0.72
DME (Li-O)	‒0.82	‒0.83	‒0.70	‒0.80
LiO₂
ACN (Li-N)	‒0.84	‒0.88	‒0.81	‒0.86
DMSO (Li-O)	‒0.98	‒1.01	‒0.94	‒1.00
DME (Li-O)	‒1.05	‒1.06	‒0.95	‒1.14

Table 2 Bond lengths in Å for the interactions of Li and LiO2 with electrolyte molecules obtained from DFT calculations. As far as the Li?O distances with respect to the complexes of LiO2 with DMSO and DME are concerned, the first line presents the Li distance to the oxygen atoms of the solvent molecules and the second line the Li?O distance within LiO2. The O?O distance always refers to the LiO2 compound.

Electrolyte	PBE	PBE-D3	RPBE	RPBE-D3
Li
ACN (Li-N)	1.94	1.94	1.99	2.00
DMSO (Li-O)	1.80	1.80	1.85	1.82
DME (Li-O)	1.98	1.99	2.00	2.04
LiO₂
ACN (Li-N)	2.07	2.04	2.16	2.05
Li-O	1.82	1.81	1.83	1.83
O-O	1.36	1.37	1.37	1.37
(DMSO) Li-O	1.88	1.90	1.92	1.91
Li-O	1.81	1.82	1.83	1.83
O-O	1.37	1.37	1.37	1.37
(DME) Li-O	2.06	2.16	2.12	2.09
Li-O	1.83	1.83	1.84	1.83
O-O	1.37	1.37	1.37	1.38

Fig. 1. Charge density difference ∆ρ upon the interaction of Li with ACN (a), DMSO (b) and DME (c) molecules, and LiO2 with ACN (d), DMSO (e) and DME (f) molecules, as obtained from DFT calculations using Eq. (2). Cyan and yellow regions correspond to electron accumulation and depletion, respectively. The isosurface levels are ±0.005 eV Å-3.

Fig. 2. Radial distribution functions of the Li?O and Li?N distances, respectively, obtained from AIMD simulations of Li (a) and LiO2 (b) in 1 mol/L ACN, DMSO and DME electrolytes. Insets show the first solvation shells for each case.

Fig. 3. Solvation energies obtained from AIMD simulations of Li (a) and LiO2 (b) in 1 mol/L of each of ACN, DMSO and DME electrolytes.

Fig. 4. Mean square displacement (MSD) obtained from AIMD simulations of Li (a) and LiO2 (b) in 1 mol/L of each of ACN, DMSO and DME electrolytes.

Fig. 5. Reaction energy barriers obtained from the Blue Moon method of AIMD simulations for (Association) Li + O2- → LiO2) (a) and (Disproportionation) 2(LiO2) → Li2O2 + O2 (b) in vacuum and 1 mol/L of each of ACN, DMSO and DME electrolytes.

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利用第一性原理模拟研究Li和LiO₂的溶剂化结构和动力学及其在非水有机电解质溶剂中的转化

Solvation structure and dynamics of Li and LiO₂and their transformation in non-aqueous organic electrolyte solvents from first-principles simulations

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